EP0081633B1 - A method of forming a patterned photoresist layer - Google Patents
A method of forming a patterned photoresist layer Download PDFInfo
- Publication number
- EP0081633B1 EP0081633B1 EP82108257A EP82108257A EP0081633B1 EP 0081633 B1 EP0081633 B1 EP 0081633B1 EP 82108257 A EP82108257 A EP 82108257A EP 82108257 A EP82108257 A EP 82108257A EP 0081633 B1 EP0081633 B1 EP 0081633B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- resist
- baking
- copolymer
- light
- exposure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- This invention relates to a method of forming a patterned photoresist layer.
- EP-A1-0064864 discloses a method of forming a patterned resist by prebaking a layer of a copolymer of methacrylonitrile and methacrylic acid, exposing the layer to a pattern of electron beam irradiation, developing the exposed copolymer layer and postbaking the copolymer layer to remove any residual developer.
- US-A-3715242 discloses a method of forming a pattern in a polymethylmethacrylate (PMMA) resist layer formed on the surface of silicon oxide.
- PMMA polymethylmethacrylate
- the PMMA layer is baked before it is exposed to an electron beam. After development of the exposed resist, it is baked again to render it sufficiently insoluble in an acid solution used to etch the silicon oxide.
- a method of forming a patterned photoresist by pattern-wise exposing a layer of resist material to light characterised in that the method comprises employing as the resist a copolymer of methacrylonitrile and methacrylic acid, baking the resist before exposure to increase its photosensitivity, exposing the resist with ultraviolet light, developing the resist with a solvent, and baking the developed resist to increase its resistance to reactive ion etching.
- the process of the present invention is very useful in photolithography employing deep ultra violet light, i.e., light around 250 nm.
- deep ultra violet light i.e., light around 250 nm.
- a positive photoresist is obtained.
- the resist becomes a negative resist.
- a key feature of the present invention is the baking process, which takes place in two stages: one before the exposure to light and the other after the resist has been imagewise exposed to light, developed, but before the resist is subjected to reactive ion etching.
- the first baking for increased photosensitivity should last from about 10 minutes to about 30 minutes and be at a temperature of from about 120°C to about 140°C.
- the second baking for high reactive ion etching resistance should last about 30 minutes at a temperature of from about 140°C to about 150°C.
- the resists of the present invention may be employed using a sensitizer when it is so desired. Particularly good results have been obtained using as a sensitizer p-t-butyl bensoic acid.
- the copolymers used in the present invention were synthesized from the freshly distilled monomers with benzoyl perioxide as a catalyst; the polymerization was carried out in vacuum at 60 to 65°C.
- the copolymer of (1:1) methacrylonitrile-methacrylic acid (on a molar basis) or of a higher content of methacrylonitrile appears to be best suited for our purpose.
- the results shown in this application are those with the (1:1) copolymer.
- the copolymer was dissolved in diglyme; 20% solid part in solution was used.
- the films were spin-coated at 1800 rpm for 1 minute onto a silicon wafer.
- the films were prebaked in air for 10 minutes at 127°C.
- t-butylbenzoic acid was added up to 10% of the solid part of the resist solution.
- the ultra-violet light exposures were carried out with a medium pressure mercury lamp (Hanovia SH-type, 120 watts input energy) or a low pressure mercury lamp (GE Germicidal lamp, 15 watts) through a quartz mask or a copper grid wire.
- a deep ultra violet photomask has been made with a quartz substrate from a common photomask, which does not transmit light below 300 nm.
- a contact printing mode was used to get high resolution patterns.
- PMMA films were spin-coated from a chlorobenzene solution, and developed in chlorobenzene.
- the photosensitivity criteron is the exposure time required to get the same remaining film thickness (-111m) of the resist after complete development. Such comparison of the exposure time has been carried out for the samples exposed to deep ultra violet light under the identical condition.
- the equipment for RIE resistance measurement has a 30,5 cm (12 inch) diameter target in a diode type system.
- Ion Etching (RIE) resistance measurements 500 volt bias potential at 150 watt operating power has been established.
- the CF 4 gas pressure was maintained at 3,3 x 1 0-2 Pa.
- the relative etch resistance has been measured either by weight loss of the resist films coated on aluminium wafers or on silicon wafers, or by an end-point detector; both results agree with each other within an experimental error.
- the pre-baked copolymer (methacrylonitrile-methacrylic acid) has a new ultra violet absorption spectrum with the maximum at 246 nm, which is absent in the original copolymer. This new ultraviolet absorption is the basis of the photosensitivity.
- the RIE resistance of the copolymer (methacrylonitrile-methacrylic acid) after heating at 120°C is far better than PMMA and poly(methyl-isopropyl-ketone).
- the copolymer (methacrylonitrile-methacrylic acid) required only 1/10 or less the exposure time to develop the polymer patterns completely in comparison with PMMA.
- the photosensitized copolymer with 10% t-butylbenzoic acid requires only 1/120 or less the exposure time relative to PMMA. This result indicates that the copolymer has a sensitivity at least 10 times or more higher than PMMA, and the photosensitized copolymer has at least 120 times higher sensitivity than PMMA.
- the polymer patterns were post-baked at 145°C for 30 minutes.
- the Si0 2 /Si patterns obtained by the CF 4 - plasma do not have scallop. The etching took place more isotropically. In the plasma, the resist films were extremely etch resistant: the patterns were made after 30 min CF 4 -plasma, followed subsequently by oxygen plasma for 20 minutes.
- the wafers were processed exactly in the same way as described above prior to the exposure. Different from the previous case, an ordinary Pyrex photo-mask with cut-off at 300 nm was used. In the 253,7 nm exposure, we have used a quartz mask which was made from the present Pyrex photomask by aluminium deposition. Thus, negative photoresists with a Pyrex photomask and positive photoresists with the quartz mask should provide the same patterns. This has happened, as shown in SEM pictures.
- the copolymer (methacrylonitrile-methacrylic acid) has 10% p-t-butyl-benzoic acid as a sensitizer; because the copolymer prior to baking does not have any uv-absorption above 280 nm the uv-absorption is solely due to the sensitizer, t-butyl benzoic acid.
- the benzoic acid has a weak absorption around 300 nm extending to 320 nm.
- the polymer yielded negative patterns with vertical or slightly undercutting wall-profiles which were suited for a single step lift-off process. In all other negative photoresists, sloped wall-profiles are obtained. Even positive photoresists never gave such vertical wall-profiles except deep ultra violet photoresists.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/330,103 US4389482A (en) | 1981-12-14 | 1981-12-14 | Process for forming photoresists with strong resistance to reactive ion etching and high sensitivity to mid- and deep UV-light |
US330103 | 1981-12-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0081633A1 EP0081633A1 (en) | 1983-06-22 |
EP0081633B1 true EP0081633B1 (en) | 1985-12-27 |
Family
ID=23288323
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82108257A Expired EP0081633B1 (en) | 1981-12-14 | 1982-09-08 | A method of forming a patterned photoresist layer |
Country Status (4)
Country | Link |
---|---|
US (1) | US4389482A (es) |
EP (1) | EP0081633B1 (es) |
JP (1) | JPS58115435A (es) |
DE (1) | DE3268140D1 (es) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2121197A (en) * | 1982-05-26 | 1983-12-14 | Philips Electronic Associated | Plasma-etch resistant mask formation |
US4572890A (en) * | 1983-05-11 | 1986-02-25 | Ciba-Geigy Corporation | Process for the production of images |
US4552833A (en) * | 1984-05-14 | 1985-11-12 | International Business Machines Corporation | Radiation sensitive and oxygen plasma developable resist |
DE3446074A1 (de) * | 1984-12-18 | 1986-06-19 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V., 3400 Göttingen | Verfahren zur herstellung von roentgen-resists |
EP0238690B1 (en) * | 1986-03-27 | 1991-11-06 | International Business Machines Corporation | Process for forming sidewalls |
DE3701569A1 (de) * | 1987-01-21 | 1988-08-04 | Basf Ag | Copolymerisate mit o-nitrocarbinolestergruppierungen, deren verwendung sowie verfahren zur herstellung von halbleiterbauelementen |
JP2506800B2 (ja) * | 1987-07-31 | 1996-06-12 | 松下電子工業株式会社 | レジストパタ−ンの形成方法 |
EP0396538A4 (en) * | 1988-01-13 | 1990-12-27 | Eastman Kodak Company | Method of making a thin lens |
JPH02251961A (ja) * | 1989-03-27 | 1990-10-09 | Matsushita Electric Ind Co Ltd | パターン形成方法 |
US5061604A (en) * | 1990-05-04 | 1991-10-29 | Minnesota Mining And Manufacturing Company | Negative crystalline photoresists for UV photoimaging |
US5079130A (en) * | 1990-05-25 | 1992-01-07 | At&T Bell Laboratories | Partially or fully recessed microlens fabrication |
EP0524759A1 (en) * | 1991-07-23 | 1993-01-27 | AT&T Corp. | Device fabrication process |
US6540928B1 (en) | 1999-09-10 | 2003-04-01 | Unaxis Usa Inc. | Magnetic pole fabrication process and device |
US6547975B1 (en) | 1999-10-29 | 2003-04-15 | Unaxis Usa Inc. | Magnetic pole fabrication process and device |
US20070259457A1 (en) * | 2006-05-04 | 2007-11-08 | Texas Instruments | Optical endpoint detection of planarization |
KR101594723B1 (ko) | 2011-08-18 | 2016-02-16 | 애플 인크. | 양극 산화 및 도금 표면 처리 |
US9683305B2 (en) * | 2011-12-20 | 2017-06-20 | Apple Inc. | Metal surface and process for treating a metal surface |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0064864A1 (en) * | 1981-05-07 | 1982-11-17 | Honeywell Inc. | Method of making sensitive positive electron beam resists |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2887376A (en) * | 1956-01-26 | 1959-05-19 | Eastman Kodak Co | Photographic reproduction process using light-sensitive polymers |
GB1328803A (en) * | 1969-12-17 | 1973-09-05 | Mullard Ltd | Methods of manufacturing semiconductor devices |
US3914462A (en) * | 1971-06-04 | 1975-10-21 | Hitachi Ltd | Method for forming a resist mask using a positive electron resist |
BE791212A (fr) * | 1972-02-03 | 1973-03-01 | Buckbee Mears Co | Procede pour le durcissement des reserves |
US3770433A (en) * | 1972-03-22 | 1973-11-06 | Bell Telephone Labor Inc | High sensitivity negative electron resist |
US3984582A (en) * | 1975-06-30 | 1976-10-05 | Ibm | Method for preparing positive resist image |
US4024293A (en) * | 1975-12-10 | 1977-05-17 | International Business Machines Corporation | High sensitivity resist system for lift-off metallization |
US4080246A (en) * | 1976-06-29 | 1978-03-21 | Gaf Corporation | Novel etching composition and method for using same |
US4132586A (en) * | 1977-12-20 | 1979-01-02 | International Business Machines Corporation | Selective dry etching of substrates |
US4184909A (en) * | 1978-08-21 | 1980-01-22 | International Business Machines Corporation | Method of forming thin film interconnection systems |
JPS5553328A (en) * | 1978-10-17 | 1980-04-18 | Oki Electric Ind Co Ltd | Production of integrated circuit element |
JPS5569265A (en) * | 1978-11-15 | 1980-05-24 | Hitachi Ltd | Pattern-forming method |
JPS6053867B2 (ja) * | 1979-09-12 | 1985-11-27 | 沖電気工業株式会社 | ネガ型フオトレジストパタ−ンの形成方法 |
JPS56100417A (en) * | 1980-01-16 | 1981-08-12 | Fujitsu Ltd | Forming method for resist pattern |
-
1981
- 1981-12-14 US US06/330,103 patent/US4389482A/en not_active Expired - Lifetime
-
1982
- 1982-09-08 EP EP82108257A patent/EP0081633B1/en not_active Expired
- 1982-09-08 DE DE8282108257T patent/DE3268140D1/de not_active Expired
- 1982-10-08 JP JP57176501A patent/JPS58115435A/ja active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0064864A1 (en) * | 1981-05-07 | 1982-11-17 | Honeywell Inc. | Method of making sensitive positive electron beam resists |
Also Published As
Publication number | Publication date |
---|---|
DE3268140D1 (en) | 1986-02-06 |
JPS58115435A (ja) | 1983-07-09 |
JPH0216911B2 (es) | 1990-04-18 |
EP0081633A1 (en) | 1983-06-22 |
US4389482A (en) | 1983-06-21 |
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